NO743491L - - Google Patents
Info
- Publication number
- NO743491L NO743491L NO743491A NO743491A NO743491L NO 743491 L NO743491 L NO 743491L NO 743491 A NO743491 A NO 743491A NO 743491 A NO743491 A NO 743491A NO 743491 L NO743491 L NO 743491L
- Authority
- NO
- Norway
- Prior art keywords
- methylene
- deoxy
- minutes
- demethyl
- tetracyclines
- Prior art date
Links
- 239000004098 Tetracycline Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 229940040944 tetracyclines Drugs 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical group C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- OUULRIDHGPHMNQ-UHFFFAOYSA-N stibane Chemical group [SbH3] OUULRIDHGPHMNQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical group [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 claims description 3
- 238000005695 dehalogenation reaction Methods 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000003003 phosphines Chemical group 0.000 claims description 2
- 230000002829 reductive effect Effects 0.000 claims description 2
- 229960002180 tetracycline Drugs 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 239000002798 polar solvent Substances 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 235000019364 tetracycline Nutrition 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910000074 antimony hydride Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003522 tetracyclines Chemical class 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- -1 organic acid salts Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229960004368 oxytetracycline hydrochloride Drugs 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006894 reductive elimination reaction Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 229930101283 tetracycline Natural products 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
Fremgangsmåte for fremstilling Method of manufacture
av 6-demethyl-6-deoksy-6-metylen-tetracykliner. of 6-demethyl-6-deoxy-6-methylene-tetracyclines.
Foreliggende oppfinnelse angår en fremgangsmåte for fremstilling av 6-demetyl-6-deoksy-6-metylen-tetracykliner ved hjelp av en dehalogenering av de tilsvarende llå-halogen-6-demetyl-6-deoksy-6-metylen-tetracykliner. The present invention relates to a method for the production of 6-demethyl-6-deoxy-6-methylene tetracyclines by means of a dehalogenation of the corresponding 10-halo-6-demethyl-6-deoxy-6-methylene tetracyclines.
Mer eksakt angår foreliggende fremgangsmåte en reduktiv dehalogenering som kan utføres ved hjelp av et tertiært fosfin ellerBEsin eller stibin, i et inert oppløsningsmiddel. More precisely, the present method concerns a reductive dehalogenation which can be carried out with the help of a tertiary phosphine or BEsine or stibine, in an inert solvent.
Man går ut fra forbindelser av følgende type:The starting point is connections of the following type:
hvor where
X = halogen,X = halogen,
R = H, OH, -0-CO-R' (R' = en alkylgruppe med fra 1 til 6 C-atomer), Y = H, halogen, R = H, OH, -0-CO-R' (R' = an alkyl group with from 1 to 6 C atoms), Y = H, halogen,
eller går ut fra deres mineral salter eller organiske syresalter, eller fra deres komplekser med salter av polyvalente metaller, hvorved man får fremstilt de tilsvarende 6-metylen-ettracykliner av følgende type: or starts from their mineral salts or organic acid salts, or from their complexes with salts of polyvalent metals, whereby the corresponding 6-methylene-tetracyclines of the following type are produced:
hvor Y og R har forannevnte betydning. where Y and R have the aforementioned meaning.
Forbindelser med formel II er kjente antibiotika, og de har spesielt verdifull aktivitet overfor mange patogene organismer, Compounds of formula II are known antibiotics, and they have particularly valuable activity against many pathogenic organisms,
og det er i britisk patent nr. 951.663, 995,031 og U.S-patent nr. 2.984.686 og tysk patent nr. 2.037.292 gitt en beskrivelse av deres fremstilling ved hjelp av reduksjonsmidler, såsom natriumhydrosulfitt, sinkpulver i surt miljø samt hydrogen & nærvær av edelmetallksatalysatorer. Foreliggende oppfinnelse er basert på at man under passende betingelser bruker tertiære fosfiner, arsiner eller stibiner for å frembringe en reduktiv eliminering av .-halogenatornet ved lia. and in British Patent No. 951,663, 995,031 and U.S. Patent No. 2,984,686 and German Patent No. 2,037,292 a description is given of their production by means of reducing agents, such as sodium hydrosulphite, zinc powder in an acidic environment as well as hydrogen & presence of noble metal catalysts. The present invention is based on using, under suitable conditions, tertiary phosphines, arsines or stibines to produce a reductive elimination of the .-halogen atom at lia.
Spesielt kan man angi trifenylfosfin som reagerer ved hjelp av følgende skjema: In particular, one can specify triphenylphosphine which reacts using the following scheme:
hvor where
X = halogen.X = halogen.
Ved hjelp av foreliggende fremgangsmåte kan en forbindelseBy means of the present method, a compound can
av gruppen tetracykliner med generell formel I og en støkiometrisk mengde av et tertiært fosfin, arsin eller stibin bringes i kontakt méd hverandre i et passende oppløsningsmiddel ved egnet tempera-tur og konsentrasjon i et tilstrekkelig langt tidsrom til at man oppnår en fullstendig omdannelse til den tilsvarende forbindelse med formel II. of the group of tetracyclines of general formula I and a stoichiometric amount of a tertiary phosphine, arsine or stibine are brought into contact with each other in a suitable solvent at a suitable temperature and concentration for a sufficiently long period of time to achieve a complete conversion to the corresponding compound of formula II.
Vanlige kjente fremgangsmåter -brukes for å skille 6-demetyl-6-deoksy-6-metylen-tetracyklinene fra reaksjonsoppløsningen. Common known methods are used to separate the 6-demethyl-6-deoxy-6-methylene-tetracyclines from the reaction solution.
Egnede oppløsningsmidler er mono- eller polyhydroksylerte alkoholer med fra 1 til h karbonatomer, metoksyetanol, etoksy-etanol og deres blandinger med dioksan, tetrahydrofuran, aceto-nitril, N,N'-dimetyl-formamid, og aceton. Suitable solvents are mono- or polyhydroxylated alcohols with from 1 to h carbon atoms, methoxyethanol, ethoxyethanol and their mixtures with dioxane, tetrahydrofuran, acetonitrile, N,N'-dimethylformamide, and acetone.
Reaksjonshastigheten og omdannelsesgraden er avhengig av temperaturen: ved temperaturer lavere enn 20°C er reaksjonen meget langsom, mens man ved temperaturer over 80°C kan frembringe dekompo-nering av utgangsforbindelsen. De foretrukne temperaturer ligger således mellom 20°C og 80°C. The reaction rate and degree of conversion depend on the temperature: at temperatures lower than 20°C the reaction is very slow, while at temperatures above 80°C decomposition of the starting compound can be produced. The preferred temperatures are thus between 20°C and 80°C.
Den réaksjonstid som er nødvendig for å få en fullstendig omdannelse er avhengig av temperaturen, men ligger vanligvis i området fra 30 - 60 minutter. The reaction time required to obtain a complete conversion depends on the temperature, but is usually in the range of 30 - 60 minutes.
Reaksjonen utføres i en inert gassatmosfære for å hindre et nærvær av oksygen som ellers ville omdanne trifenylfosfinet til det inaktive trifenylfosfinoksyd. The reaction is carried out in an inert gas atmosphere to prevent the presence of oxygen which would otherwise convert the triphenylphosphine into the inactive triphenylphosphine oxide.
Den optimale mengde trifenylfosfin er 1 mol pr, mol av tetra-cyklinet, mindre mengder fører til en ufullstendig omdannelse og større mengder gir ingen fordeler. The optimum amount of triphenylphosphine is 1 mol per mole of the tetracycline, smaller amounts lead to incomplete conversion and larger amounts provide no benefit.
De fremstilte 6-demetyl-6-deoksy-6-metylen-tetracyklinerThey prepared 6-demethyl-6-deoxy-6-methylene tetracyclines
kan utkrystalliseres som hydroklorid med utmerkede analytiske egenskaper direkte fra den ubrukte reaksjonsoppløsningen. can be crystallized as hydrochloride with excellent analytical properties directly from the unused reaction solution.
De følgende eksempler illustrerer oppfinnelsen.The following examples illustrate the invention.
Eksempel I.Example I.
h0,5 g Ph^P ble tilsatt 100 g lla-klor-6-demetyl-6-deoksy-6-metylen-5-oksytetracyklin-p-toluensulfonat i 950 ml MeOH. h0.5 g of Ph^P was added to 100 g of lla-chloro-6-dimethyl-6-deoxy-6-methylene-5-oxytetracycline-p-toluenesulfonate in 950 ml of MeOH.
Oppløsningen ble oppvarmet til 60°C, holdt under røring iThe solution was heated to 60°C, maintained under stirring i
30 minutter og så konsentrert ved lavt trykk til 250 ml.30 minutes and then concentrated at low pressure to 250 ml.
Man tilsatte deretter 250 ml Me2C0 og 100 ml 37 f» HC1.250 ml of Me2C0 and 100 ml of 37% HCl were then added.
Den. resulterende oppløsning ble holdt i 30 minutter vedIt. resulting solution was kept for 30 minutes at
6o°C under raring, og etter langsom avkjøling til 10 - 15°C utførte man en filtrering, og bunnfallet ble vasket med aceton og vakuum- . tørket ved k0°C. Man fikk i alt 6l,5 g 6-demetyl-6-deoksy-6-metylen-5-oksy-tetracyklin med en spektrofotometrisk verdi på 6o°C under stirring, and after slow cooling to 10 - 15°C, filtration was carried out, and the precipitate was washed with acetone and vacuum- . dried at k0°C. A total of 61.5 g of 6-demethyl-6-deoxy-6-methylene-5-oxy-tetracycline with a spectrophotometric value of
98 98
Eksempel II.Example II.
20,8 g lla-klor-6-demetyl-6-deoksy-6-metylen-5-oksytetracyklin-hydrofluorid i en blanding av 50 ml MeOH og 50 ml Me^CO, ble tilsatt 11 g Ph^P og oppvarmet til 60°C. 20.8 g of lla-chloro-6-demethyl-6-deoxy-6-methylene-5-oxytetracycline hydrofluoride in a mixture of 50 ml of MeOH and 50 ml of Me^CO was added to 11 g of Ph^P and heated to 60 °C.
Etter 30 minutter avkjølte man oppløsningen til 20°C og tilsatte 30 rnl 37 $'s HC1, oppvarmet det hele til 50°C og etter 60 min. ble det langsomt avkjølt til 15-20°C. Man utførte så en filtrering og vasking av bunnfallet med aceton. After 30 minutes the solution was cooled to 20°C and 30 ml of 37$'s HC1 was added, the whole was heated to 50°C and after 60 min. it was slowly cooled to 15-20°C. The precipitate was then filtered and washed with acetone.
Det fremstilte produkt ble vakuumtørket ved 50°C og veietThe produced product was vacuum dried at 50°C and weighed
l6,l g og ga en spektrofotometrisk verdi på 98,5 $.l6.l g and gave a spectrophotometric value of $98.5.
Eksempel III♦ 8 g lla-brom-6-demetyl-6-deo.ksy-6-metylen-5-oksytetracyklin, vannfritt, ble oppløst i 80 ml THF og 20 ml MeOH, hvoretter man tilsatte k g Ph^P og holdt det hele på Ko°C i 2 timer.. Example III♦ 8 g of lla-bromo-6-dimethyl-6-deoxy-6-methylene-5-oxytetracycline, anhydrous, were dissolved in 80 ml of THF and 20 ml of MeOH, after which k g of Ph^P were added and kept whole at Ko°C for 2 hours..
Etter dette tidsrom fant man at det hadde skjedd en nesten fullstendig omdannelse til 6-demetyl-6-deoksy-6-metylen-5-oksy-tetracyklin. After this time it was found that an almost complete conversion to 6-demethyl-6-deoxy-6-methylene-5-oxy-tetracycline had taken place.
Eksempel IV.Example IV.
h , 88 g lla-f luor-6-demetyl-6-deo.ksy-6-metylen-5-oksytetracyklin-hydrofluorid ble behandlet som angitt i eksempel II. Man fikk i alt 4,1 g 6-demetyl-6-deoksy-6-metylen-5-oksytetracyklin-hydroklorid som ga en spektrofotometrisk prøveverdi på 97,5 h , 88 g of 11a-fluoro-6-demethyl-6-deoxy-6-methylene-5-oxytetracycline hydrofluoride was treated as indicated in Example II. A total of 4.1 g of 6-demethyl-6-deoxy-6-methylene-5-oxytetracycline hydrochloride was obtained, which gave a spectrophotometric test value of 97.5
Eksempel V.Example V.
69,2 g lla-klor-6-demetyl-6-deoksy-6-metylen-5-acetoksytetra-cyklin-mesylat ble behandlet med 26,2 g Eh^P i kokende MeOH. 69.2 g of 11a-chloro-6-dimethyl-6-deoxy-6-methylene-5-acetoxytetracycline mesylate was treated with 26.2 g of Eh 2 P in boiling MeOH.
Man fikk en fullstendig omdannelse etter 30 minutter. A complete transformation was achieved after 30 minutes.
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT2948873 | 1973-09-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO743491L true NO743491L (en) | 1975-04-28 |
Family
ID=11227078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO743491A NO743491L (en) | 1973-09-28 | 1974-09-26 |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US3962330A (en) |
| JP (1) | JPS5062969A (en) |
| AT (1) | AT337893B (en) |
| AU (1) | AU7381574A (en) |
| BE (1) | BE820475A (en) |
| CA (1) | CA1118770A (en) |
| DE (1) | DE2446588A1 (en) |
| DK (1) | DK501474A (en) |
| ES (1) | ES430510A1 (en) |
| FR (1) | FR2246537B1 (en) |
| IL (1) | IL45740A0 (en) |
| NL (1) | NL7412763A (en) |
| NO (1) | NO743491L (en) |
| SE (1) | SE7412217L (en) |
| ZA (1) | ZA746121B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4987242A (en) * | 1988-10-28 | 1991-01-22 | Jagmohan Khanna | Hydrogenation catalyst useful in the production of alpha-6-deoxytetracyclines |
| AU2005244988C1 (en) | 2004-05-21 | 2012-06-28 | President And Fellows Of Harvard College | Synthesis of tetracyclines and analogues thereof |
| JP5335664B2 (en) * | 2006-04-07 | 2013-11-06 | プレジデント アンド フェロウズ オブ ハーバード カレッジ | Synthesis of tetracycline and its analogs. |
| US7763735B2 (en) * | 2006-10-11 | 2010-07-27 | President And Fellows Of Harvard College | Synthesis of enone intermediate |
| EP2424834B1 (en) | 2009-04-30 | 2018-07-11 | President and Fellows of Harvard College | Synthesis of tetracyclines and intermediates thereof |
| CN107827823B (en) * | 2017-11-22 | 2020-01-31 | 大连奇凯医药科技有限公司 | Preparation method of 4, 5-dibromoimidazole |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3250809A (en) * | 1962-09-06 | 1966-05-10 | Pfizer & Co C | 6-deoxy-6-demethyl-6-halomethylene tetracyclines and their 11a-chloro and fluoro derivatives |
| US3649700A (en) * | 1966-12-20 | 1972-03-14 | Knapsack Ag | Process for the dehydrochlorination of chlorinated hydrocarbons |
| US3659006A (en) * | 1969-06-17 | 1972-04-25 | Borg Warner | Synthesis of alpha-haloacrylonitrile |
-
1974
- 1974-09-24 DK DK501474A patent/DK501474A/da not_active Application Discontinuation
- 1974-09-24 US US05/509,054 patent/US3962330A/en not_active Expired - Lifetime
- 1974-09-25 CA CA000210078A patent/CA1118770A/en not_active Expired
- 1974-09-25 IL IL45740A patent/IL45740A0/en unknown
- 1974-09-26 AT AT776474A patent/AT337893B/en not_active IP Right Cessation
- 1974-09-26 NO NO743491A patent/NO743491L/no unknown
- 1974-09-26 ZA ZA00746121A patent/ZA746121B/en unknown
- 1974-09-27 SE SE7412217A patent/SE7412217L/xx unknown
- 1974-09-27 BE BE149014A patent/BE820475A/en unknown
- 1974-09-27 NL NL7412763A patent/NL7412763A/en unknown
- 1974-09-28 JP JP49112211A patent/JPS5062969A/ja active Pending
- 1974-09-28 ES ES430510A patent/ES430510A1/en not_active Expired
- 1974-09-30 FR FR7432898A patent/FR2246537B1/fr not_active Expired
- 1974-09-30 DE DE19742446588 patent/DE2446588A1/en active Pending
- 1974-09-30 AU AU73815/74A patent/AU7381574A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2446588A1 (en) | 1975-04-03 |
| FR2246537B1 (en) | 1978-08-11 |
| IL45740A0 (en) | 1974-11-29 |
| US3962330A (en) | 1976-06-08 |
| DK501474A (en) | 1975-05-26 |
| CA1118770A (en) | 1982-02-23 |
| NL7412763A (en) | 1975-04-02 |
| AT337893B (en) | 1977-07-25 |
| ATA776474A (en) | 1976-11-15 |
| BE820475A (en) | 1975-01-16 |
| AU7381574A (en) | 1976-04-01 |
| ES430510A1 (en) | 1976-10-01 |
| SE7412217L (en) | 1975-04-01 |
| ZA746121B (en) | 1975-11-26 |
| JPS5062969A (en) | 1975-05-29 |
| FR2246537A1 (en) | 1975-05-02 |
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